Disazo dye compounds



Patented May 13, 1947 DISAZO DYE COMPOUNDS George J. Taylor, Rochester,Eastman Kodak Company,

N. Y., assignor to Rochester, N. Y., a

corporation of New Jersey No Drawing. Application August 15, 1942,Serial No. 454,905

l Claim. 1

This invention relates to new substantive disazo dye compounds.

t is an object of my invention to provide new disazo dye compounds.Another object is to provide new disazo dye compounds useful in colorphotography. A further object of my invention is to provide disazo dyecompounds which color cotton and wool. A still further object is toprovide a satisfactory method for the preparation of the new disazo dyecompounds.

The new disazo dye compounds have the general formula:

wherein R- =l lrepresents the residue of a member selected from thegroup consisting of a diazotized monocyclic aminoaryl nucleus of thebenzene'series and a diazotized aminonaphthalene nucleus, said memberhaving a substituent selected from the groupconsisting of an amido groupand a sulfonamido group attached directly through nitrogen to itsnucleus, R'l-N=N-- represents the residue of a diazotized memberselected from the group consisting of a l-amino- 2,5-dialkoxybenzene anda l-amino-Z-alkoxynaphthalene and R2 represents the residue of a memberselected from the group consisting of a 2- henzoylamino- 8-'-hydroxynaphthalene-6-sulfonic a Z-acylamino 8 hydroxynaphthalene-G-sulfonic acid, a 2-benzoylamino 8-hydroxynaphtha1ene-3,6-disulfonicacid, a Z-acylaminQ-S hydroxynaphthalene-Ii,fi-disulfonic acid, aZ-benzoylamino-6-hydroxynaphthalene-8-sulfonic acid and a 2acylamino-fi-hydroxynaphthalene 8-sulfonic acid.

While my invention relates azo dye compounds having the above formula,it relates more particularly to those compounds in which at least one ofthe members R and R1 contain a nuclear sulfonic acid group and in whichthe amide grouping or the sulfonamido grouping is attached to thebenzene or naphthalene nucleus R in para position to the azo bond.Normally, the amide grouping joined to the benzene or naphthalenenucleus R is an alkylamido group represented by the formula:

broadly to the dis- The new disazo dye compounds of my invention areuseful in processes of color photography depending upon the chemicalbleaching. of dyes in the presence of developed silver images. Thus,they are useful inthe color photography process disclosed in ChristensenU. S. Patent 1,517,049, issued November 5, 1924. Further, they areuseful in the color photogrpahy process disclosed in the copendingEhrenfried application Serial No.

360,622, filed October 10, 19 10 (now United States Patent 2,322,001,dated June 15, 1943). The disazo dye compounds of my invention do notdiffuse through set gelatin and, therefore, require no precipitatingagent to prevent diffusion. Fur ther, these new disazo dyes possessdesirable spectral obsorption properties, for example, for the cyan(blue-green) dye in three-color photography. The new disazo dyecompounds of the invention carrbe used in suitable color-photographyprocesses as either image or filter dyes. They are especially of use asimage dyesinmulti layer color films. In addition to their utility forcolor photography purposes, the new disazo dyes likewise can be employedto color cotton and wool.

The-new disazo dye compounds of .my .inven-: tion can be prepared bydiazotizing the monocyclic aminobenzene or aminonaphthalene nucleusdefined hereinbefore, coupling the. diazonium compound obtained with a1-amino-2-alkoxynaphthalene or a1-amin0-2,5 dia1koxybenzene, diazotizingthe monoazo dye thus formed and coupling the diazonium compound obtainedwith a 2-benzoylamino-8-hydroxynaphthalene-6- sulfonic acid, a2-acylamino-8-hydroxynaphthalene-G-sulfonic acid, a Z-benzoylamino-Bhydroxynaphthalene-3,6-disulfonic acid, a Z-acylamino 8hydroxynaphthalene 3,6 disulfonic acid, a2-benzoylamino-S-hydroxynaphthalene-S sulfonic acid or a2-acylamino-S-hydroxynaphthalene-8-sulfonic acid.

As first components that can be employed in the preparation of thedisazo dye compounds of the invention may be mentionedp-aminoacetanilide, m-aminoacetanilide,2-amino-5-acetaminobenzenesulfonic acid, 2-acetamino-5aminobenzenesulfonic acid, 1 amino i-oxalylaminoben- Zone, 2 oxalylamino5 aminobenzenesulfonic acid, 2-amino-5-oxalylaminobenzenesulfonic acid,1 amino 3 propionylaminobenzene, 1 aminol-butyrylaminobenzene, 1aminol-(N-methyl- N-acetyl-) -aminobenzene, l-amino 4benzoylaminobenzene, 1-amino-2-benzoylaminobenzene,

N-(p-aminophenyl) -succinimlde, N (p aminophenyl) -maleinimide.

0 ll 0-011 C) H2N- -N i 2 0-0 Lamino-i- -N\ CH: benzene a-(n1, 0

Q l-(4-aminophenyl) -3-methyl-5 pyrazolone, N p-aminophenyl)-2-pyrrolidone, l-aminol-methylsulfonylaminobenzene H (HzN-ON-S 02cm) Nphenylsulfonyl) -p-phenylenediamine, l-amino-4-ethylsulfonylaminobenzene, 1 amino 4- butylsulfonylaminobenzene, N-(p-toluene-sulfonyl-p-phenylenediamine, l-amino-l-cetylsulfonyll amino 2ethylsulfonylaminobenzene, l-amino-3-methylsulfonylaminobenzene,

(butyl, amyl, heXyl, octyl, decyl or cetyD-benzene,1-amino-4-acetaminonaphthalene, l-amino-4-acetaminonaphthalene-G-sulfonic acid,l-amino-4-acetaminonaphthalene-7-sulfonic acid, 1-

amino-4-benzoylaminonaphhtalene, l-amino 4- 0benzoylaminonaphthalene-6-sulfonic acid,l-amino-4-benzoylaminonaphthalene '7 sulfonic acid and1-amino-2-p-toluenesulfonylaminonaphthalenc.

Second components that can be employed inelude, for example,l-amino-2-ethoxynaphthalene, 1 amino 2-ethoxynaphthalene-6-sulfonicacid, 1 amino 2-ethoxynaphthalene-7-su1fonic acid,l-amino-2-methoxynaphthalene, l-amino- 2-propoxynaphthalene-6-sulfonicacid, 1-amino- 40 2-butoXynaphthalene-7-su1fonic acid, 1-amino-2,5-dimethoxybenzene, 1-amino-2,5-dieth0xybenzene,1-amino-2,5-dipropoxybenzene, l-amino-2- ethoxy-5-methoxybenzene and1amino-2,5-dibutoxybenzene.

Third components that can be employed include, for example,2-(4"-amino-2-benzamidobenzamido) -8-hydroxynaphthalene 6 sulfonic acid,2 lamino-benzamido) -8-hydroxynaphthalene-S-sulfonic acid,droxynaphthaleneG-sulfonic acid, Z-acetamino-S-hydroxynaphthalene-S-sulfonio acid,2propionylamino-8-hydroxynaphthaiene-6 sulfonic acid, 2(4'-acetamino-benzamido)-8-hydroxynaphthalene-G-sulfonic acid,2-(4"-acetaminol-benzamido-benzamido) 8 hydrcxynaphthalene-G-sulfonicacid, 2-(2'-sulfo4-aminobenzamido) -8-hydroxynaphthalene-6 sulfonic acidand the corresponding N-benzoyl and N -acyl dcrivatives of2-amino-8-hydroxynaphthalene-3,6-

disulfonic acid and Z-amino-S-hydroxynaphthalene-S-sulfonic acid. Itwill be understood that other N-benzoyl and N-acyl derivatives can beemployed in addition to those specifically named,

as only the simpler and more common N-benzoyl 55 and N -acy1 derivativeshave been given.

cific gravity 1.18).

2-benzoylamino-8-hy- 50 It will be apparent from the illustrative firstcomponents given hereinbefore that the term amido group or amidogrouping refers broadly to groups containing wherein the member Rcontains a sulfonamido group yield magenta shades.

The following examples illustrate the preparation of the disazo dyecompounds of the invention:

Example 1 37.5 grams (.25 gram mole) of p-aminoacetanilide are dissolvedin 1000 grams of water and 60 grams of concentrated hydrochloric acid(spe- The resulting solution is cooled to 10 C. and diazotized byadding, with stirring, 17.5 grams of sodium nitrite While maintainingthe temperature at about 10 C. Stirring is continued for /2 hour aftercomplete ad dition of the sodium nitrite at the end of which time thecomplete diazotization mixture is run into a suspension of 66.8 grams(.25 gram mole) of 1-amino-2-ethoxynaphthalene-7-sulfonic acid in 500grams of Water following which 50 grams of CH3COONa.3I-I2O are added andstirring is continued for about 24 hours. The reaction mixture is thencooled to 10 C. and made alkaline by the addition of 280 grams of 10%aqueous sodium hydroxide following which it is diazotized with 35 gramsof sodium nitrite and grams of concentrated hydrochloric acid (specificgravity 1.18) Throughout the diazotization reaction the reaction mixtureis stirred while maintained at a temperature of about 10 C. Aftercompletion of the diazotization reaction which requires about two hours,the diazotization product is salted out with sodium chloride, recoveredby filtration, and placed in suflicient water at 0 C. to form a paste.This diazotization product is then coupled at a temperature of 10 C.with a solution of grams (.25 gram mole) of 2-(4"-amino- 4benzamido-benzamido) -8-hydroxynaphthalene-G-sulfonic acid in 300 gramsof pyridine and grams of an aqueous 28% ammonia solution. The reactionmixture resulting is stirred for 24 hours at the end of which time thedye compound formed is recovered by filtration. This dye compound may bepurified by salting it out of a water solution with a salt such assodium chloride. The dye obtained has in its free acid state, theformula:

SOaH

Example 2 0.25 gram mole of p-aminoacetanilide i dialotized and thediazonium compound obtained is coupled with 0.25 gram mole of 1-amino-2-thoxynaphthalene-G-sulfonic acid and the monoazo dye thus obtained is inturn diazotized and coupled with 0.25 gram mole (90 grams) of 2-(4-amino-benzamido) -8 hydroxynaphthalene fi-sulfonic acid. The dyecompound obtained has in its free acid state the formula:

OCzH5 OH CHOEONN NN I o-Qnn a 2 II I] 0 0 H033 SOaH Example 3 SOSH Thediazotization, coupling and recovery operations necessary to theformation of the dye compound of this example can be carried outfollowing the procedure described in detail in Example 1.

Example 4 7.8 grams of 1-amino-4-oxalylaminobenzene- 2-sulfonic acid aredissolved in 50 grams of water and 24.5 grams of 10% aqueous sodiumhydroxide. 2.1 grams of sodium nitrite dissolved in 20 parts of waterare then added and the resulting solution is added slowly to 9.5 gramsof concentrated hydrochloric acid (specific gravity 1.18) in 50 grams ofwater at 10 C. Stirring is continued for two hours at the end of whichtime the diazonium reaction, mixture is run into a. solution of 5.7grams of 1-amino-2-ethoxynaphthalene in grams of Water and 3.7 grams ofconcentrated sulfuric acid (specific gravity 1.84) at 15 C. The reactionmixture is stirred for about 24 hours at the end of which time it iscooled to 10 C. and made alkaline by the addition of 78' grams of a 10%aqueous sodium hydroxide solution. Following this, the reaction mixtureis diazotized with 5 grams of sodium nitrite and 33 grams ofconcentrated hydrochloric acid (specific gravity 1.18). Thediazotization is complete in about two hours at which time thediazotization product is salted out with s0- dium chloride, filtered offand placed in enough water to form a paste at 0 C. This diazotizationproduct is then coupled with a solution of 10.7 grams of2-(4-aminobenzamido) -8-hydroxynaphthalene-(i-sulfonic acid in 50 gramsof pyridine and 23 grams of 28% aqueous ammonia at 10 C. The reactionmixture is stirred for 24 hours at which time the dye is filtered offand purified by salting out of a water solution by the addition ofsodium chloride. The dye thus obtained corresponds in its free acidstate to the formula:

Example 5 0.25-gram mole of 1-amino-4-acetaminonaphthalenefl sulfonicacid is diazotized and the diazonium compound obtained is coupled with0.25 gram mole of l--amino-2-ethoxynaphthalene-5- sulfonic acid and themonoazo dye thus obtained is in turn diazotized and coupled with 0.25gram mole of .2-benzoylamino--8-hydroxynaphthalenefi-sulfonic acid. Thedye compound obtained has in its free acid state the formula:

0 0211;; OH on o g N N i H O 3 J N=N -NC H H o HOBS- o SOaH 50311 Thediazotization, coupling and recovery operations necessary to theformation of the dye compound of this example can be carried outfollowing the procedure described in detail in Example 4.

The compounds whose formulae are given here inafter can be preparedfollowing the general procedure described and illustrated in theforegoing examples. When the first diazonium component contains asulfonic acid group the procedure described in Example 4 is ordinarilyfollowed; if no sulfonic acid group is present, the general proceduredescribed in Example 1 is employed.

OCHs- SOBH I I H 2) CH3 H SOaH OCHs 502K OCH; HO-

H 0 (lg 002115 OH N N N=N- (ll) HO3S- l SOaH O OaH OH HOaS -SOaH SOaHOCH: 50311 H H H O O O 0 SOaH OCH: SOaH H H N: N=N Ni|3 N-(fll 0 O OCH:HO- HN-SGGEB The following tabulation further illustrates the compoundsof my invention. It will be understood that the components mentioned canbe combined following the general procedure described in Examples 1 to5, inclusive, or by varia tions of this procedure which are apparent tothose skilled in the art to which this invention relates.

It will be understood that the disazo dye compounds specificallydisclosed herein are intended to be illustrative and not limitative ofmy inven- 40 tion. Thus, within the teachings of the invention, thevarious componentsdisclosed herein may be combined with one another toyield the new disazo dye compounds of the invention. To illustrate,p-aminoacetanilide in Example 1 can be First Component I SecondComponent m-aminoacetanilide l-amino-2-ethoxy-naphthalone-(i-sulionicacid. N -(p-toluencsulfonyl)-p-phenylenediamme do2-acctamino-5amino-benzenesulfonic acid do. 2acetamino-5-amino-bcnzenesulfonmcthyl-amide do N-(p-aminophenyD-phthalimide do p-Aminoacetanilide l-amino-Z-ethoxynaphthalene-7-sulfoninacid. do

d0 l-(4-aminopheny1)-3-methyl-5-pyraz0l0ne l-amino-2ethoxynaphthalene-dsulfonic aci 1-(3-aminophenyl)-3-methyl-5-pyrazo1one .do1-(4-an1inophenyl)-3-carboxyl-5pyrazolone do1-(4-a!ninopl1enyl)-3-carboxylic acid ethyl ester-5-l-amino-Z-ethoxynaphthalcne-7-sulpyrazolone. ionic acid.1-(4-aminophenyl) -3-phenyl-5-pyraz0lone dol-amino-i-acetaminonaphthalene 1-amino-2-ethoxynaphthalcne-G-sulionicacid. l-aminoi-bcnzoylaminonaphthalene do1-amino-4-acetaminonaphthalene-G-sulfonic acid.--1-amino-2,5-dimethoxybenzcncl-arniinoi-benzoylaminonaphthalene-fi-sulfonic do acll-amino-ei-benzoylaminonaphthalene-7-sulfonic1-amino-2-ethoxynaphthalenc-7-sulacid. ionic acid.1-amino-2-p-toluencsulfonylaminonaphthalenedo Third Component c2-(4-acetaminobenzamido) lene-6-sulfonic acid.Z-bcilfizOylamino-Shydroxynaphthalene-fi-Sulionic acl2-ace5amino-8-hydroxynaphthalenc-G-sulfonic -8-hydroxynaphtha-2-(4-aminobenzamido)-8-hydroxynaphthalenc- 3,6-disuli'onic acid.

2-(4-amin0-2-sulfonic acid benzamido)-8-hy lroxynaphtl1aIene-6-sulfonicacid.

2-(4-aminobenzamido)-8-hydroxynaphthalcne-6- sulionic acid.

2- (4-acctaminobenzamido)-8-hydroxynaphthalenc-6-sulfonic acid.

2- (4-acetan1inobenzainido)-8-hydroxynaphthaleue-3,6 disulfonic acid.

2-(4-aminobenzamido)-8-hydroxynaphthalcne-6- sulfonic acid.

2-benoylamino-fi-hydroxynaphthalcne-S-sulfonic aci2-(4-aminobenzamido)-8-hydroxynaphthalcne-6- sulfonic acid.

Z-propionylamino-S-hydroxynaphthalenc-6-suI- fonic acid.

2-(4-aceta1ninobenzamide)-8-hydroxynaphthalene-fi-suli'onic acid.

Z-aceamino-S-hydroxynaphthalene-3,6-disul1onic aci2-benzoy1amino-8-hydroxynaphthalene-fi-sulfonic acid.

ylamino-6-hydroxynaphthalcne-B-sulionic 801d.

9 10 replaced by an equivalent gram molecular weight otherwiseindicated, includes not only the unof any of the other first componentsto obtain substituted benzoylamino group but also subdisazo dyecompounds of the invention. That is, stituted benzoylamino groups as hasbeen indiany first component can be replaced by any other catedhereinbefore. first component, any second component can be 5 I claim:replaced y y other Second Component and any The disaZo compound havingthe formula:

0 $0113 SHO3 SIOBH third component can be replaced by any other GEORGEJ. TAYLOR. third component.

When used to color wool and cotton, the disazo NC S C TED dye Compoundsof the invention can be applied- The following references are of recordin the to these materials by methods well known to the fil f thispatent; art for coloring these materials. When the disazo dye compoundsare to be employed in color UNITED STATES PATENTS photography operationsof the character indi- Number Name Date cated hereinbefore it will beunderstood that the 2,231,149 Gaspar Apr, 28, 1942 manner of theiremployment is the same as 2,294,892 Carroll et a1. Sept. 8, 1942described in the patents and applications referred 1,877,303 Gr therSept. 13, 1932 to. 1,699,427 Fellmer Jan. 15, 1929 When used inphotographic emulsion layers, 1,855,963 I-Ientrich et al Apr. 26, 1932the dyes of my invention are incorporated in 1,150,675 Gunther Aug. 17,1915 amounts of from about 2.5 grams to 25 grams 2,265,425 Fischer eta1. Dec, 9, 1941 of dye per 100 grams of gelatin. The emulsions1,947,027 W odward Feb. 13, 193 1 are coated to give a dye concentrationof from 0.15 to 1.5 grams of dye per square meter of FOREIGN PATENTSemulsion surface. Number Country Date It will be understood that theterm benzoyl- 259,970 Great Britain Jan. 13, 1928 amino as used hereinand in the claim, unless 3 273,932 Germany May 11, 1914 Certificate ofCorrection Patent No. 2,420,630. May 13, 1947.

GEORGE J. TAYLOR It is hereby certified that errors appear in theprinted specification of the above numbered patent requiring correctionas follows: Column 2, line 40, for 1-amin0-3 read Lamina-4; column 10,in the claim, for that portion of the formula reading SI-I0 read H80 andthat the said Letters Patent should be read with these ggrectionstherein that the same may conform to the record of the case in thePatent Signed and sealed this 15th day of July, A. D. 1947. 7

LESLIE FRAZER,

First Assistant Commissioner of Patents.

